145175-64-0Relevant academic research and scientific papers
Vanadium-substituted MCM-41 zeolites as catalysts for oxidation of alkanes with peroxides
Neumann, Ronny,Khenkin, Alexander M.
, p. 2643 - 2644 (1996)
Alkanes are oxidized selectively to ketones using V-MCM-41 with isobutyraldehyde/dioxygen as the preferred oxidant in terms of product selectivity and catalyst stability and recycle.
Ruthenium colloids: A new catalyst for alkane oxidation by tBHP in a biphasic water-organic phase system
Launay, Franck,Roucoux, Alain,Patin, Henri
, p. 1353 - 1356 (2007/10/03)
Efficient and highly selective conversion of cyclooctane into cyclooctanone is obtained under pure biphasic conditions through t-butylhydroperoxide activation by the in situ formation of colloidal ruthenium species arising from RuCl3, 3H2O. Model extension experiments to other cycloalkanes are also discussed.
A putative monooxygenase mimic which functions via well-disguised free radical chemistry
MacFaul, Philip A.,Ingold,Wayner,Que Jr., Lawrence
, p. 10594 - 10598 (2007/10/03)
The hydroxylation of cycloalkanes at 25°C by the syringe pump addition of tert-alkyl hydroperoxides (10 and 1 equiv based on catalyst) to deoxygenated acetonitrile containing cycloalkanes (0.64 M) and 0.61 mM of the catalyst, [Fem(III)2O(TPA)2(H2O)2]4+, is demonstrated to be a reaction which involves freely diffusing cycloalkyl radicals, i.e., free alkyl radicals.
Oxygen activation by metal complexes and alkyl hydroperoxides. Applications of mechanistic probes to explore the role of alkoxyl radicals in alkane functionalization
MacFaul, Philip A.,Arends, Isabella W. C. E.,Ingold, Keith U.,Wayner, Danial D. M.
, p. 135 - 146 (2007/10/03)
The mechanism of the oxidation of cycloalkanes by tertiary alkyl hydroperoxides catalysed by iron(III) dichlorotris(2-pyridylmethyl)amine IIICl2(TPA)>+ and by the acetate bridged (μ-oxo) di-iron complex III(TPA)2O(OAc)>3+ has been investigated.Product studies do not support oxidation via a high valent iron-oxo intermediate (formally FeV=O), but are consistent with a mechanism involving hydrogen atom abstraction from the alkane by alkoxyl radicals derived from the hydroperoxide.In the presence of a large excess of tert-butyl hydroperoxide, the oxidation of cyclohexane yields cyclohexanone, cyclohexanol and tert-butylcyclohexyl peroxide in more than stoichiometric amounts and, in the case of the mono-iron catalyst, one equivalent of cyclohexyl choride.Replacement of Me3COOH by hydroperoxides, which could yield tert-alkoxyl radicals having much shorter lifetimes than the tert-butoxyl radical prevents oxidation of the cycloalkane.The products obtained with these hydroperoxide mechanistic probes are those derived from the fast unimolecular reactions (generally β-scissions) of the corresponding alkoxyl radicals.The inapplicability of dimethyl sulfide as a mechanistically diagnostic trap for the putative FeV=O intermediate and the value of di-tert-butyl hyponitrite as a non-iron-based source of tert-butoxyl radicals are discussed.
The Role of Alkoxyl Radicals in Gif (GoAggv) Chemistry
Snelgrove, Darren W.,MacFaul, Philip A.,Ingold, Keith U.,Wayner, Danial D. M.
, p. 823 - 826 (2007/10/03)
The oxidation of cyclooctane using tert-alkyl hydroperoxides under GoAggv conditions has been examined using selected alkyl hydroperoxides as mechanistic probes. The results indicate that the products are formed by alkoxyl radical-induced reactions, there being no need to invoke any chemistry involving high valent iron-oxo species.
The functionalization of saturated hydrocarbons. Part 24. The use of tert-butyl hydroperoxide: GoAggIV and GoAggV
Barton, Derek H. R.,Chavasiri, Warinthorn
, p. 19 - 30 (2007/10/02)
The use of tert-butyl hydroperoxide as an oxidant in Gif-type systems (GoAggIV and GoAgfV) catalyzed by various Fe(III) species is examined. Regioselectivity studids of these systems have revealed several characteristics similar to those observed for other prdviously reported Gif-type reactions. A common rdaction pathway for the GoAggIV and GoAggV oxidation systems and other Gif-type reactions (from alkane via alkyl hydroperoxide to ketone or alcohol) is seen.
The functionalization of saturated hydrocarbons. Part 25. Ionic substitution reactions in GoAggIV chemistry: The formation of carbon-halogen bonds
Barton, Derek H. R.,Beviere, Stephane D.,Chavasiri, Warinthorn
, p. 31 - 46 (2007/10/02)
GoAggIV chemistry (Fe (III) species, tert-butyl hydroperoxide in a mixture of pyridine and acetic acid) in the presence of LiCl can transform saturated hydrocarbons efficiently into the corresponding alkyl chlorides. The transformation into monosubstituted alkyl derivatives by "ionic trapping" reagents arising from the interception of the first intermediate of the system supports the presence of a high valent VFe-C species. Mechanistic studies suggest a possible pathway operating via an Fe-centered ligand coupling. In addition, the production of alkyl chlorides and alkyl bromides could also be achieved employing this system in the presence of halogenating reagents such as CCl4 and BrCCl3.
Comments on An Article by Francesco Minisci and Francesca Fontana.
Barton, Derek H. R.,Hill, David R.
, p. 1431 - 1434 (2007/10/02)
Evidence is summarized to show that the least aspects of Gif chemistry do not involve Fenton-type radical chemistry.
The Fe(III)-Catalyzed Functionalization of Saturated Hydrocarbons by tert-Butyl Hydroperoxide: Mechanistic Studies on the Role of Dioxygen
Barton, Derek H. R.,Beviere, Stephane D.,Chavasiri, Warinthorn,Doller, Dario,Hu, Bin
, p. 5473 - 5476 (2007/10/02)
The Fe(III)-catalyzed ketonization of saturated hydrocarbons by tert-butyl hydroperoxide (TBHP) in pyridine-acetic acid or acetonitrile solution follows the reaction pathway alkane -> alkyl hydroperoxide -> ketone or alcohol.Dioxygen (O2) is the precursor of the oxygen atoms in the alkyl hydroperoxide, the alcohol, and the ketone.
